Vacancy titanates intercalated with cationic hydroxy aluminum complexes

ABSTRACT

There is provided a vacancy titanate intercalated with a cationic hydroxy aluminum complex, such as a Keggin ion. A method for making this material and a process for using this material as a catalyst are also provided.

This application is a division of copending U.S. application Ser. No.07/896,850, filed Jun. 12, 1992, now U.S. Pat. No. 5,256,617, which is acontinuation-in-part of copending U.S. application Ser. No. 07/636,856,filed Jan. 2, 1991, now U.S. Pat. No. 5,155,076, the entire disclosuresof which are expressly incorporated herein by reference.

BACKGROUND

There is provided a vacancy titanate intercalated with a cationichydroxy aluminum complex, such as a Keggin ion. A method for making thismaterial and a process for using this material as a catalyst are alsoprovided.

Many layered materials are known which have three-dimensional structureswhich exhibit their strongest chemical bonding in only two dimensions.In such materials, the stronger chemical bonds are formed intwo-dimensional planes and a three-dimensional solid is formed bystacking such planes on top of each other. However, the interactionsbetween the planes are weaker than the chemical bonds holding anindividual plane together. The weaker bonds generally arise frominterlayer attractions such as Van der Waals forces, electrostaticinteractions, and hydrogen bonding. In those situations where thelayered structure has electronically neutral sheets interacting witheach other solely through Van der Waals forces, a high degree oflubricity is manifested as the planes slide across each other withoutencountering the energy barriers that arise with strong interlayerbonding. Graphite is an example of such a material. The silicate layersof a number of clay materials are held together by electrostaticattraction mediated by ions located between the layers. In addition,hydrogen bonding interactions can occur directly between complementarysites on adjacent layers, or can be mediated by interlamellar bridgingmolecules.

Laminated materials such as clays may be modified to increase theirsurface area. In particular, the distance between the interlamellarlayers can be increased substantially by absorption of various swellingagents such as water, ethylene glycol, amines, ketones, etc., whichenter the interlamellar space and push the layers apart. However, theinterlamellar spaces of such layered materials tend to collapse when themolecules occupying the space are removed by, for example, exposing theclays to high temperatures. Accordingly, such layered materials havingenhanced surface area are not suited for use in chemical processesinvolving even moderately severe conditions.

The extent of interlayer separation can be estimated by using standardtechniques such as X-ray diffraction to determine the basal spacing,also known as "repeat distance" or "d-spacing". These values indicatethe distance between, for example, the uppermost margin of one layerwith the uppermost margin of its adjoining layer. If the layer thicknessis known, the interlayer spacing can be determined by subtracting thelayer thickness from the basal spacing.

Various approaches have been taken to provide layered materials ofenhanced interlayer distance having thermal stability. Most techniquesrely upon the introduction of an inorganic "pillaring" agent between thelayers of a layered material. For example, U.S. Pat. No. 4,216,188incorporated herein by reference discloses a clay which is cross-linkedwith metal hydroxide prepared from a highly dilute colloidal solutioncontaining fully separated unit layers and a cross-linked agentcomprising a colloidal metal hydroxide solution. However, this methodrequires a highly dilute forming solution of clay (less than 1g/l) inorder to effect full layer separation prior to incorporation of thepillaring species, as well as positively charged species of crosslinking agents. U.S. Pat. No. 4,248,739, incorporated herein byreference, relates to stable pillared interlayered clay prepared fromsmectite clays reacted with cationic metal complexes of metals such asaluminum and zirconium. The resulting products exhibit high interlayerseparation and thermal stability.

U.S. Pat. No. 4,176,090, incorporated herein by reference, discloses aclay composition interlayered with polymeric cationic hydroxy metalcomplexes of metals such as aluminum, zirconium and titanium. Interlayerdistances of up to 16A are claimed although only distances restricted toabout 9A are exemplified for calcined samples. These distances areessentially unvariable and related to the specific size of the hydroxymetal complex.

Silicon-containing materials are believed to be a highly desirablespecies of intercalating agents owing to their high thermal stabilitycharacteristics. U.S. Pat. No. 4,367,163, incorporated herein byreference, describes a clay intercalated with silica by impregnating aclay substrate with a silicon-containing reactant such as an ionicsilicon complex, e.g., silicon acetylacetonate, or a neutral speciessuch as SiCl₄. The clay may be swelled prior to or during siliconimpregnation with a suitable polar solvent such as methylene chloride,acetone, benzaldehyde, tri- or tetraalkylammonium ions, ordimethylsulfoxide. This method, however, appears to provide only amonolayer of intercalated silica resulting in a product of small spacingbetween layers, about 2-3 A as determined by X-ray diffraction.

U.S. Pat. No 4,859,648 describes layered oxide products of high thermalstability and surface area which contain interlayer polymeric oxidessuch as polymeric silica. These products are prepared by ion exchanginga layered metal oxide, such as layered titanium oxide, with organiccation, to spread the layers apart. A compound such astetraethylorthosilicate, capable of forming a polymeric oxide, isthereafter introduced between the layers. The resulting product istreated to form polymeric oxide, e.g., by hydrolysis, to produce thelayered oxide product. The resulting product may be employed as acatalyst material in the conversion of hydrocarbons.

U.S. Pat. Nos. 4,831,005; 4,831,006 and 4,929,587, the entiredisclosures of which are expressly incorporated herein by reference,describe various methods for intercalating layered materials termedtitanometallate-type layered metal oxides, wherein each layer of themetal oxide has the general formula

[M_(x) _(y) Z₂₋(x+y) 0₄ ]^(q-)

wherein M is at least one metal of valence n wherein n is an intergerbetween 0 and 7, represents a vacancy site, Z is titanium, and wherein

    q=4y-x(n-4)0<x+y<2

These intercalating methods involve the placement of polymeric oxides,such as silica, between the layers of the layered material.

SUMMARY

There is provided a layered metal oxide material, wherein each layer ofthe metal oxide has the general formula

[ _(y) Ti_(2-y) 0₄ ]^(q-)

where 0<y<2 and q=4y, said layered material being intercalated with acationic hydroxy aluminum complex.

There is also provided a method for intercalating a layered metal oxidematerial, wherein each layer of the metal oxide has the general formula

[ _(y) Ti_(2-y) 0₄ ]^(q-)

where 0<y<2 and q=4y, said method comprising the steps of:

(i) swelling the said layered material by contacting said layeredmaterial with organoammonium cations; and

(ii) contacting the swollen layered material of step (i) with a cationichydroxy aluminum complex.

There is further provided a process for converting an organic compound,said process comprising contacting an organic compound under sufficientconversion conditions with a layered metal oxide material, wherein eachlayer of the metal oxide has the general formula

[ _(y) Ti_(2-y) 0₄ ]^(q-)

where 0<y<2 and q=4y, said layered material being intercalated with acationic hydroxy aluminum complex.

EMBODIMENTS

The present invention takes advantage of a direct pillaring procedureunder aqueous conditions to form alumina-vacancy titanate products. TheX-ray patterns for phases with high alumina contents clearly showd-spacings at approximately 15 Angstroms corresponding to the vacancytitanate layers separated by the alumina particles. The phasescontaining low amounts of alumina (<10%Al), however, form verydisordered structures (virtually X-ray amorphous; lacking a peak atapproximately 15 Angstroms) with higher surface areas and sorptioncapacities. The latter group of materials are unique because they arenot representative of classical pillared products as judged from theirX-ray patterns. This latter group of materials may have less than 10 wt.% of Al, e.g., from 5 to 8 wt. % of Al, as measured by elementalanalysis.

The layered materials, which may be intercalated by methods describedherein, are described in copending U.S. application Ser. No. 587,481,filed Sep. 21, 1990, and in PCT International Publication Number WO88/00090, published Jan. 14, 1988, as well as in the aforementioned U.S.Pat. Nos. 4,831,005; 4,831,006 and 4,929,587. The layered materialsdescribed in these disclosures comprise a layered metal oxide, whereineach layer of the metal oxide has the general formula

[M_(x) _(y) Z₂₋(x+y) 0₄ ]^(q-)

wherein M is at least one metal of valence n wherein n is an integerbetween 0 and 7 and preferably is 2 or 3, represents a vacancy site, Zis a tetravalent metal, preferably titanium, and wherein

    q=4y-x(n-4) and preferably is 0.6-0.9, 0<x+y<2

The layered materials, which are intercalated in accordance with thepresent disclosure, correspond to the materials of the above formula,wherein x is zero and Z is Ti. Such materials are referred to herein asvacancy titanates.

It is to be appreciated that the term "layered" metal oxide is usedherein in its commonly accepted sense to refer to a material whichcomprises a plurality of separate metal oxide layers which are capableof being physically displaced away from one another such that thespacing between adjacent layers is increased. Such displacement can bemeasured by X-ray diffraction techniques and/or by density measurements.

The present layered material may be made from a vacancy titanatestarting material which contains anionic sites having interspathiccations associated therewith. Such interspathic cations may includehydrogen ion, hydronium ion and alkali metal cation.

More specifically, the present invention employs a layered metal oxidestarting material in which each layer has the general formula

[ _(y) Ti_(2-y) 0₄ ]^(q-)

where 0<y<2 and q=4y.

Interposed between the layers of the oxide will be charge-balancingcations A of charge m wherein m is an integer between 1 and 3,preferably 1. Preferably A is a large alkali metal cation selected fromthe group consisting of Cs, Rb and K. Structurally, these metal oxidesconsist of layers of ( _(y) Ti_(1-y))O.sub. 6 octahedra which are transedge-shared in one dimension and cis edge-shared in the second dimensionforming double octahedral layers which are separated by the A cations inthe third dimension. These materials can be prepared by high temperaturefusion of a mixture of 1) alkali metal carbonate or nitrate and 2)titanium dioxide. Such fusion can be carried out in air in ceramiccrucibles at temperatures ranging between 600° to 1100° C. after thereagents have been ground to an homogeneous mixture. The resultingproduct is ground to 20 to 250 mesh, preferably about 100 mesh, prior tothe organic swelling and intercalcation steps.

Further description of various titanometallate-type layered materialsand their methods of preparation can be found in the followingreferences:

Reid, A. F.; Mumme, W. G.; Wadsley, A. D. Acta Cryst. (1968), B24, 1228;Groult, D.; Mercy, C.; Raveau, B. J. Solid State Chem. 1980, 32 289;England, W. A.; Burkett, J. E.; Goodenough; J. B., Wiseman, P. J. J.Solid. State Chem. 1983, 49 300. The infinite trans-edge shared layerstructure of the vacancy titanates instead of the sheared 3-blockstructure of, for example, Na₂ Ti₃ O₇, or the sheared 4-block structureof, for example, K₂ Ti₄ O₉, may reduce or eliminate shearing of thelayers as a possible mechanism for thermal or hydrothermal decompositionof the calcined intercalated material.

The layered metal oxide starting material may be initially treated witha "propping" agent comprising a source of organic cation, such asorganoammonium cation, in order to effect an exchange of theinterspathic cations resulting in the layers of the starting materialbeing propped apart. Suitable organoammonium cations include such asn-dodecylammonium, n-octylammonium, n-heptylammonium, n-hexylammonium,n-butylammonium and n-propylammonium. During this propping or swellingstep it is important to maintain a low hydrogen ion concentration toprevent decomposition of the vacancy titanate structure as well as toprevent preferential sorption of hydrogen ion over the propping agent. ApH range of 6 to 10, preferably 7 to 8.5 is generally employed duringtreatment with the propping agent.

The foregoing treatment results in the formation of a layered metaloxide of enhanced interlayer separation depending upon the size of theorganic cation introduced. In one embodiment, a series of organic cationexchanges can be carried out. For example, an organic cation may beexchanged with an organic cation of greater size, thus increasing theinterlayer separation in a step-wise fashion.

After the ion exchange, the organic-"propped" species may be treatedwith a solution of a cationic hydroxyaluminum complex. Such complexesand solutions thereof are described in U.S. Pat. No. 4,176,090, theentire disclosure of which is expressly incorporated herein byreference. These complexes may have the formula Al.sub. 2+n (OH)_(3n)X₆, wherein n has a value from 4 to 12 and X is selected from the groupconsisting of Cl, Br, NO₃ and CO₃. Upon hydrolysis up to about 10% ofthe aluminum of these complexes may be tetrahedrally coordinated, theremainder of the aluminum being octahedrally coordinated. An example ofthe hydrolyzed complex is a Keggin ion of the formula

[Al₁₃ 0₄ (OH)₂₄ (H₂ O)₁₂ ]⁷⁺

It is preferred that the organic cation deposited between the layers becapable of being removed from the pillared material without substantialdisturbance or removal of the interspathic aluminum. For example,organic cations such as n-octylammonium may be removed by exposure toelevated temperatures, e.g., calcination, in nitrogen or air, or bychemical oxidation.

These layered products, especially when calcined, exhibit high surfacearea and thermal and hydrothermal stability making them highly useful ascatalysts or catalytic supports, for hydrocarbon conversion processes.

After calcination to remove the organic propping agent, the finalpillared product may contain residual exchangeable cations. Suchresidual cations in the layered material can be ion exchanged by knownmethods with other cationic species to provide or alter the catalyticactivity of the pillared product. Suitable replacement cations includecesium, cerium, cobalt, nickel, copper, zinc, manganese, platinum,lanthanum, aluminum, ammonium, hydronium and mixtures thereof.

The layered material catalyst described herein can optionally be used inintimate combination with a hydrogenating component such as tungsten,vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or anoble metal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponent can be exchanged into the composition, impregnated therein orintimately physically admixed therewith. Such component can beimpregnated in, or on, the layered material such as, for example, by, inthe case of platinum, treating the layered material with a solutioncontaining a platinum metal-containing ion. Thus, suitable platinumcompounds for this purpose include chloroplatinic acid, platinouschloride and various compounds containing the platinum amine complex.

The layered material may be subjected to thermal treatment, e.g., todecompose organoammonium ions. This thermal treatment is generallyperformed by heating one of these forms at a temperature of at leastabout 370° C. for at least 1 minute and generally not longer than 20hours. While subatmospheric pressure can be employed by the thermaltreatment, atmospheric pressure is preferred simply for reasons ofconvenience.

Prior to its use in organic conversion processes described herein, thelayered material catalyst should usually be dehydrated, at leastpartially. This dehydration can be done by heating the crystals to atemperature in the range of from about 200° C. to about 595° C. in anatmosphere such as air, nitrogen, etc., and at atmospheric,subatmospheric or superatmospheric pressures for between about 30minutes and to about 48 hours. Dehydration can also be performed at roomtemperature merely by placing the layered material in a vacuum, but alonger time is required to obtain a sufficient amount of dehydration.

The layered material catalyst can be shaped into a wide variety ofparticle sizes. Generally speaking, the particles can be in the form ofa powder, a granule, or a molded product such as an extrudate having aparticle size sufficient to pass through a 2 mesh (Tyler) screen and beretained on a 400 mesh (Tyler) screen. In cases where the catalyst ismolded, such as by extrusion, the layered material can be extrudedbefore drying or partially dried and then extruded.

It may be desired to incorporate the layered material with anothermaterial which is resistant to the temperatures and other conditionsemployed in the catalytic processes described herein. Such materialsinclude active and inactive materials and synthetic or naturallyoccurring zeolites as well as inorganic materials such as clays, silicaand/or metal oxides such as alumina. The latter may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. Use of a material in conjunctionwith layered material, i.e., combined therewith or present during itssynthesis, which itself is catalytically active may change theconversion and/or selectivity of the catalyst. Inactive materialssuitably serve as diluents to control the amount of conversion so thatproducts can be obtained economically and orderly without employingother means for controlling the rate of reaction. These materials may beincorporated into naturally occurring clays, e.g., bentonite and kaolin,to improve the crush strength of the catalyst under commercial operatingconditions. Said materials, i.e., clays, oxides, etc., function asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in commercial use, it is desirable toprevent the catalyst from breaking down into powder-like materials.These clay binders have been employed normally only for the purpose ofimproving the crush strength of the catalyst.

Naturally occurring clays which can be composited with layered materialsinclude the montmorillonite and kaolin family, which families includethe subbentonites, and the kaolins commonly known as Dixie, McNamee,Georgia and Florida clays or others in which the main mineralconstituent is halloysite, kaolinite, dickite, nacrite, or anauxite.Such clays can be used in the raw state as originally mined or initiallysubjected to calcination, acid treatment or chemical modification.Binders useful for compositing with layered materials also includeinorganic oxides, notably alumina.

In addition to the foregoing materials, the layered materials can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia.

The relative proportions of finely divided layered materials andinorganic oxide matrix vary widely, with the layered material contentranging from about 1 to about 90 percent by weight and more usually,particularly when the composite is prepared in the form of beads, in therange of about 2 to about 80 weight of the composite.

The layered material of the present invention is useful as a catalystcomponent for a variety of organic, e.g. hydrocarbon, compoundconversion processes. Such conversion processes include, as non-limitingexamples, cracking hydrocarbons with reaction conditions including atemperature of from about 300° C. to about 700° C., a pressure of fromabout 0.1 atmosphere (bar) to about 30 atmospheres and a weight hourlyspace velocity of from about 0.1 to about 20; dehydrogenatinghydrocarbon compounds with reaction conditions including a temperatureof from about 300° C. to about 700° C., a pressure of from about 0.1atmosphere to about 10 atmospheres and a weight hourly space velocity offrom about 0.1 to about 20; converting paraffins to aromatics withreaction conditions including a temperature of from about 100° C. toabout 700° C., a pressure of from 0.1 atmosphere to about 60atmospheres, a weight hourly space velocity of from about 0.5 to about400 and a hydrogen/hydrocarbon mole ratio of from about 0 to about 20;converting olefins to aromatics, e.g. benzene, toluene and xylenes, withreaction conditions including a temperature of from about 100° C. toabout 700° C., a pressure of from about 0.1 atmosphere to about 60atmospheres, a weight hourly space velocity of from about 0.5 to about400 and a hydrogen/hydrocarbon mole ratio of from about 0 to about 20;converting alcohols, e.g. methanol, or ethers, e.g. dimethylether, ormixtures thereof to hydrocarbons including aromatics with reactionconditions including a temperature of from about 300° C. to about 550°C., more preferably from about 370° C. to about 500° C., a pressure offrom about 0.01 psi to about 2000 psi, more preferably from about 0.1psi to about 500 psi, and a liquid hourly space velocity of from about0.5 to about 100; isomerizing xylene feedstock components with reactionconditions including a temperature of from about 230° C. to about 510°C., a pressure of from about 3 atmospheres to about 35 atmospheres, aweight hourly space velocity of from about 0.1 to about 200 and ahydrogen/hydrocarbon mole ratio of from about 0 to about 100;disproportionating toluene with reaction conditions including atemperature of from about 200° C. to about 760° C., a pressure of fromabout atmospheric to about 60 atmospheres and a weight hourly spacevelocity of from about 0.08 to about 20; alkylating aromatichydrocarbons, e.g. benzene and alkylbenzenes, in the presence of analkylating agent, e.g. olefins, formaldehyde, alkyl halides andalcohols, with reaction conditions including a temperature of from about340° C. to about 500° C., a pressure of from about atmospheric to about200 atmospheres, a weight hourly space velocity of from about 2 to about2000 and an aromatic hydrocarbon/alkylating agent mole ratio of fromabout 1/1 to about 20/1; and transalkylating aromatic hydrocarbons inthe presence of polyalkylaromatic hydrocarbons with reaction conditionsincluding a temperature of from about 340° C. to about 500° C., apressure of from about atmospheric to about 200 atmospheres, a weighthourly space velocity of from about 10 to about 1000 and an aromatichydrocarbon/polyalkylaromatic hydrocarbon mole ratio of from about 1/1to about 16/1.

In the Examples which follow, whenever sorption data are set forth forcomparison of sorptive capacities for water, cyclohexane and/orn-hexane, they were equilibrium adsorption values determined as follows:

A weighted sample of the calcined adsorbent was contacted with thedesired pure adsorbate vapor in an adsorption chamber, evacuated to lessthan 1 mm and contacted with 21 Torr of water vapor and 40 Torr ofn-hexane or cyclohexane vapor, pressures less than the vapor-liquidequilibrium pressure of the respective adsorbate at 90° C. The pressurewas kept constant (within about ±0.5 mm) by addition of adsorbate vaporcontrolled by a mamostat during the adsorption period, which did notexceed about 8 hours. As adsorbate was adsorbed by the layered material,the decrease in pressure caused the manostat to open a valve whichadmitted more adsorbate vapor to the chamber to restore the abovecontrol pressures. Sorption was complete when the pressure change wasnot sufficient to activate the manostat. The increase in weight wascalculated as the adsorption capacity of the sample in g/100 of calcinedadsorbant.

All of the following Examples utilized a vacancy titanate (VT) swelledby octylamine. The attempted composition was Cs₀.7 []₀.175 Ti₁.825 O₄(Cs_(x) [Ti₂₋(x/4) []_(x/4) ]O₄,[]=vacancy, x=0.7), and was synthesizedby high-temperature solid state reaction of Cs₂ CO₃ and TiO₂.Stoichiometric amounts of the starting materials to give theabove-mentioned attempted composition were thoroughly mixed by grinding,and the mixture was heated at 650° C. for 20 h. The mixture was groundand heated 3 to 4 times to ensure complete reaction. The ammoniumexchange process was carried out by repeated refluxing of the aboveproduct in 1 M NH₄ NO₃. The NH₄ ⁺ -exchanged VT was swelled by refluxingthe solid in octylamine (b.p. 175-176° C.) for 24 hr.

EXAMPLE 1

AlCl₃ 6H₂ O(4.83 g) was dissolved in ca. 250 ml H₂ O/EtOH (10:1)mixture. A second solution was prepared by adding 6.35 g octylamine to50 ml of H₂ O/EtOH (1:1) mixture. The amine solution as then addeddropwise to the aluminum chloride solution. The resulting cloudysolution was aged for ca. 30 minutes, followed by the addition of 1.5 goctylamine-swelled VT. The mixture was heated to 70° C. while stirring.After 18 hr., the reaction was stopped, the mixture was centrifuged andwashed 5 times followed by filtering the final solid and washing withmore H₂ O. The product was calcined at 500° C. The results of sorptionand elemental analysis are summarized in Table 1.

The X-ray diffraction pattern of the calcined product showed a peak atapproximately 15 Angstroms, corresponding to the separation of thetitanate layers (7 Angstroms thick) by the hydroxyl aluminum species.

EXAMPLE 2

2.90 g of hydrated aluminum hydroxychloride, i.e. MicroDry (AluminumChlorhydrol, 46.2% Al oxide, Reheis Chemical Company) was dissolved inca. 25 ml H₂ O. This solution was stirred for ca. 45 min. In a separatecontainer, 1.0 g octylamine-swelled VT was mixed with ca. 25 ml H₂ O.The first solution was added to the VT suspension dropwise. The finalmixture was heated to 60° C. The reaction was stopped after 19 hr. Theproduct was centrifuged and washed 3 times followed by filtering thefinal solid and washing with more H₂ O. The product was calcined at 500°C. The results of sorption and elemental analysis are summarized inTable 1.

The X-ray diffraction pattern of the calcined product showed a peak atapproximately 15 Angstroms, corresponding to the separation of thetitanate layers (7 Angstroms thick) by the hydroxyl aluminum species.

EXAMPLE 3

0.55 g MicroDry (Aluminum Chlorhydrol, 46.2% Al oxide, Reheis ChemicalCompany) was dissolved in ca. 15 ml H₂ O. This solution was stirred forca. 30 min. In a separate container, 1.9 g octylamine-swelled VT wasmixed with ca. 50 ml H₂ O. The first solution was added to the VTsuspension dropwise. The final mixture was heated to 60° C. The reactionwas stopped after 42 hr. The product was centrifuged and washed 3 timesfollowed by filtering the final solid and washing with more H₂ O. Theproduct was calcined at 500° C. The results of sorption and elementalanalysis are summarized in Table 1.

The X-ray powder diffraction pattern did not contain a peakcorresponding to the intercalated product indicating the formation of adisordered composite.

EXAMPLE 4

0.28 g MicroDry (Aluminum Chlorhydrol, 46.2% Al oxide, Rebels ChemicalCompany) was dissolved in ca. 25 ml H₂ O. This solution was stirred forca. 30 min. In a separate container, 2.0 g octylamine-swelled VT wasmixed with ca. 50 ml H₂ O. The first solution was added to the VTsuspension dropwise. The final mixture was heated to 60° C. The reactionwas stopped after 17 hr. The product was centrifuged and washed 3 timesfollowed by filtering the final solid and washing with more H₂ O. Theproduct was calcined at 500° C. The results of sorption and elementalanalysis are summarized in Table 1.

The X-ray powder diffraction pattern did not contain a peakcorresponding to the intercalated product indicating the formation of adisordered composite.

                  TABLE 1                                                         ______________________________________                                        Elemental Analysis and Sorption Data for A1-VT Products                                                           sorption                                  Sample    A1/c.e.s..sup.a                                                                          % A1.sup.b                                                                             S.A..sup.c                                                                          capacity.sup.d                            ______________________________________                                        EXAMPLE 1 4.61       17.55    35.   3.7                                       EXAMPLE 2 9.13       15.88    67.   6.6                                       EXAMPLE 3 0.91        7.18    111.  6.2                                       EXAMPLE 4 0.44        6.16    101.  7.4                                       ______________________________________                                         .sup.a Ratio of A1 to the cation exchange sites in VT (during synthesis)      .sup.b Aluminum content as determined by elemental analysis                   .sup.c BET surface area (m.sup.2 /g)                                          .sup.d cyclohexane sorption (wt. %)                                      

What is claimed is:
 1. A process for converting a hydrocarbon compound,said process comprising contacting a hydrocarbon compound undersufficient conversion conditions with a layered metal oxide material,wherein each layer of the metal oxide has the general formula[ _(y)Ti_(2-y) 0₄ ]⁻⁹ where represents a vacancy site, 0<y<2 and q=4y, saidlayered material being intercalated with a cationic hydroxy aluminumcomplex.
 2. A process according to claim 1, wherein said cationichydroxy aluminum complex is a Keggin ion.
 3. A process according toclaim 1, wherein said cationic hydroxy aluminum complex has the formulaAl.sub. 2+n (OH)_(3n) X₆, wherein n has a value of 4 to 12 and X isselected from the group consisting of Cl, Br, NO₃ and CO₃.
 4. A processaccording to claim 3, wherein up to about 10% of the aluminum of thecationic hydroxy aluminum complex is tetrahedrally coordinated.
 5. Aprocess according to claim 1, wherein the intercalated layered metaloxide comprises less than 10 wt. % of Al and the X-ray diffractionpattern of this intercalated layered metal oxide does not have peak at15 Angstroms.
 6. A process according to claim 5, wherein theintercalated layered metal oxide comprises between 5 and 8 wt. % of Al.